CN115710023A - Preparation method of high-nickel anode material of lithium ion battery and high-nickel anode material of lithium ion battery prepared by using preparation method - Google Patents

Preparation method of high-nickel anode material of lithium ion battery and high-nickel anode material of lithium ion battery prepared by using preparation method Download PDF

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CN115710023A
CN115710023A CN202211293178.0A CN202211293178A CN115710023A CN 115710023 A CN115710023 A CN 115710023A CN 202211293178 A CN202211293178 A CN 202211293178A CN 115710023 A CN115710023 A CN 115710023A
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nickel
lithium
ion battery
lithium ion
cathode material
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CN115710023B (en
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张磊
王新鹏
何艳
张建
李锂
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Anhui Tianli Lithium Energy Co ltd
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Priority to LU504854A priority patent/LU504854B1/en
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Abstract

The invention discloses a preparation method of a high-nickel anode material of a lithium ion battery and the high-nickel anode material of the lithium ion battery prepared by the preparation method, and particularly relates to the technical field of the anode material of the lithium ion battery. The preparation method comprises the following steps: (1) Mixing a high-nickel ternary positive electrode material precursor, a lithium salt, a phosphorus-containing additive and a metal oxide additive; (2) Putting the mixed materials into a sagger, putting the sagger into a high-temperature and high-pressure device for sintering, and naturally cooling the sagger after sintering; and (3) grinding and sieving the cooled materials to obtain the material. Has the advantages that: according to the invention, the high-nickel ternary positive electrode material precursor, the lithium salt, the phosphorus-containing additive and the metal oxide additive are mixed according to a special proportion, and the mixture is sintered at low temperature and then sintered at high temperature, so that the high-nickel positive electrode material with low residual lithium, low pH value and low specific surface area is obtained, the process flow is greatly simplified, and the manufacturing cost is reduced.

Description

Preparation method of high-nickel positive electrode material of lithium ion battery and high-nickel positive electrode material of lithium ion battery prepared by using preparation method
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly discloses a preparation method of a lithium ion battery high-nickel anode material and the lithium ion battery high-nickel anode material prepared by the same.
Background
In recent years, with the rapid development of the new energy automobile industry, the demand of lithium ion batteries is rapidly increased, people have higher and higher requirements on the endurance mileage of new energy automobiles, the demand of high-energy density lithium ion batteries is rapidly increased, and the demand of high-nickel anode materials is rapidly increased along with the demand. The high-nickel ternary material has the characteristic of high capacity and also has certain defects, and Li is caused by insufficient oxidation process of divalent nickel due to higher nickel content 1+ /Ni 2+ The mixing and discharging are serious, and lithium ions cannot completely migrate into the structure, so that the content of residual lithium on the surface is high, and the performance of material capacity is influenced.
The preparation process of the high-nickel ternary cathode material mainly comprises a secondary sintering process, and comprises the following specific steps: uniformly mixing the precursor, lithium salt and additive, performing primary high-temperature sintering in a kiln, crushing, washing with water, drying, coating the surface, and performing secondary sintering; according to the method, residual lithium on the surface of the material is removed mainly through water washing, but in the water washing process, along with the removal of residual alkali, lithium ions in the structure migrate to the surface of the material, so that the stability of the interior of the structure is poor, in addition, the secondary sintering process is low-temperature sintering after boric acid coating, although the pH value of the material can be controlled to be about 11.6, the specific surface area of the material is generally larger than 0.5m 2 The method has the advantages that the material and the electrolyte have serious side reaction, the material circulation performance is seriously influenced, the manufacturing process of the method is long, the equipment investment at the early stage is large, and the manufacturing cost is extremely high.
Chinese patent application publication No. CN114933335A discloses a high-nickel ternary cathode material and a preparation method thereof, which comprises the following steps of 1, preparing a precursor, 2, preparing an oxidation solution, weighing an oxidant, dissolving the oxidant in deionized water, and adding a water-soluble alkaline substance; step 3, preparing a modified precursor; and 4, mixing a lithium source with the modified precursor to prepare the positive electrode material, and further providing the corresponding positive electrode material and the lithium battery, wherein a layer of intermediate product is formed on the surface layer of the precursor by adopting a pre-oxidation method, so that the defect of NCA surface layer crystals is eliminated, and the stability and the rate capability of the battery in the circulating process are obviously improved. However, the patent does not address the problem of removing residual lithium from the surface of the material.
Disclosure of Invention
The invention aims to solve the technical problems of high residual lithium content, high pH value and large specific surface area of the conventional high-nickel cathode material.
The invention solves the technical problems through the following technical means:
a preparation method of a high-nickel cathode material of a lithium ion battery comprises the following steps:
(1) Mixing a high-nickel ternary positive electrode material precursor, a lithium salt, a phosphorus-containing additive and a metal oxide additive; the molar ratio of the lithium element in the lithium salt to the nickel-cobalt-manganese element in the high-nickel ternary cathode material precursor is 1.00-1.10; the addition amount of the phosphorus-containing additive accounts for 0.1-1.5 wt% of the mass of the high-nickel ternary cathode material precursor; the addition amount of the metal oxide additive accounts for 0.1-0.5 wt% of the mass of the high-nickel ternary cathode material precursor;
(2) Putting the mixed material obtained in the step (1) into a sagger, putting the sagger into a high-temperature and high-pressure device for sintering, and naturally cooling the sagger after sintering;
(3) And (3) grinding and sieving the material cooled in the step (2) to obtain the high-nickel anode material of the lithium ion battery.
Has the beneficial effects that: according to the invention, a high-nickel ternary positive electrode material precursor, a lithium salt, a phosphorus-containing additive and a metal oxide additive are mixed according to a special proportion, a high-temperature high-pressure gradient sintering technology and a crystal growth control technology are used, and the characteristic that the radius of phosphate radicals and metal cations is large and the diffusion is not easy at low temperature is utilized, divalent nickel is fully oxidized into trivalent nickel under the atmosphere of low-temperature high-pressure pure oxygen, so that lithium ions can be conveniently migrated into the interior of a result, the lithium-nickel mixed discharge and the surface residual lithium are reduced, then the temperature sintering is continuously improved, the reaction speed of the residual lithium on the surface of the material and the phosphate radicals/metal ions is controlled while the primary particles of the material grow directionally, and the purpose of reducing and controlling the surface state of the material is achieved, so that the high-nickel positive electrode material with low residual lithium, low pH value and low specific surface area is obtained.
Preferably, the chemical formula of the high-nickel ternary cathode material precursor is Ni x Co y Mn z Al 1-x-y-z (OH) 2 Wherein x is more than or equal to 0.8 and less than or equal to 0.9, y is more than or equal to 0.05 and less than or equal to 0.15, z is more than or equal to 0.01 and less than or equal to 0.10, and x + y + z is more than or equal to 0.95 and less than or equal to 0.99.
Preferably, the structure of the high-nickel ternary cathode material precursor is a core-shell structure, the internal core material is a high-nickel material, the external shell material is a low-nickel high-manganese material, and the molar ratio of nickel content in the high-nickel material is more than 85% and less than 96%; wherein the molar ratio of the nickel content in the low-nickel high-manganese material is less than 60 percent, and the molar ratio of the manganese content is more than 20 percent and less than 60 percent.
Preferably, the particle size D50 of the high-nickel ternary cathode material precursor is 6-15um.
Preferably, the lithium salt is one or a combination of two of lithium hydroxide, lithium oxalate, lithium dihydrogen phosphate and lithium phosphate.
Preferably, the phosphorus-containing additive is one or more of ammonium dihydrogen phosphate, phosphorus pentoxide, titanium phosphate, aluminum phosphate and phosphotungstic acid.
Preferably, the metal oxide additive is a metal oxide additive having a metal ion radius of between 60 and 80 pm.
Preferably, the metal oxide additive is one or more of zirconium oxide, tungsten oxide, titanium oxide and strontium oxide.
Preferably, the high-temperature high-pressure sintering device is an intermittent sintering device, the maximum sintering temperature is 900 ℃, and the internal pressure of the kiln can be automatically adjusted between-10 Pa and 500Pa according to program setting.
Preferably, the sintering in step (2) is performed in an oxygen atmosphere furnace.
Preferably, the volume content of oxygen in the oxygen atmosphere furnace is more than or equal to 90 percent, and the concentration of carbon dioxide is less than 50ppm.
Preferably, the sintering in the step (2) is gradient sintering, and the low-temperature sintering is performed first, and then the high-temperature sintering is performed.
Preferably, the low-temperature sintering specifically comprises: heating to 650-780 ℃ at the heating rate of 1-3 ℃/min under the pressure of-10 to-5 Pa, and preserving heat for 4-10 h, wherein the pressure in the heat preservation process is 50-200 Pa.
Preferably, the high-temperature sintering specifically comprises: heating to 750-850 ℃ at the heating rate of 0.5-2 ℃/min under the pressure of-10 to-5 Pa, and preserving heat for 4-10 h, wherein the pressure in the heat preservation process is 5-50 Pa.
Preferably, the high-nickel cathode material with low residual lithium, low pH value and low specific surface area is obtained after high-temperature high-pressure gradient sintering is finished; the content of residual lithium on the surface of the high-nickel anode material is 500-1200 ppm; the pH value of the high-nickel anode material is between 11.30 and 11.70; the specific surface area of the high-nickel anode material is between 0.15 and 0.m 2/g.
The invention also provides the high-nickel cathode material of the lithium ion battery prepared by the preparation method.
The invention has the advantages that:
(1) According to the invention, a high-nickel ternary positive electrode material precursor, a lithium salt, a phosphorus-containing additive and a metal oxide additive are mixed according to a special proportion, a high-temperature high-pressure gradient sintering technology and a crystal growth control technology are used, and the characteristic that the radius of phosphate radicals and metal cations is large and the diffusion is not easy at low temperature is utilized, divalent nickel is fully oxidized into trivalent nickel under the atmosphere of low-temperature high-pressure pure oxygen, so that lithium ions can be conveniently migrated into the interior of a result, the lithium-nickel mixed discharge and the surface residual lithium are reduced, then the temperature sintering is continuously improved, the reaction speed of the residual lithium on the surface of the material and the phosphate radicals/metal ions is controlled while the primary particles of the material grow directionally, and the purpose of reducing and controlling the surface state of the material is achieved, so that the high-nickel positive electrode material with low residual lithium, low pH value and low specific surface area is obtained.
(2) The invention radically solves the problems of high content of residual lithium, high pH value and large specific surface area of the high-nickel cathode material, shortens the manufacturing process flow and reduces the manufacturing cost.
(3) Compared with the prior art, the method has obvious advantages, the problems of residual lithium and uncontrollable specific surface area in the industry are thoroughly solved, the process flow is greatly simplified, and the manufacturing cost has obvious advantages.
Drawings
FIG. 1 is an electron micrograph of a material obtained in example 1 of the present invention;
FIG. 2 is an electrical property diagram of the material prepared in example 1 of the present invention;
FIG. 3 is an electron micrograph of a material obtained in example 2 of the present invention;
fig. 4 is an electrical property diagram of the material prepared in example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a preparation method of a high-nickel cathode material of a lithium ion battery comprises the following steps:
(1) Mixing a high-nickel ternary positive electrode material precursor, a lithium salt, a phosphorus-containing additive and a metal oxide additive; wherein, the precursor of the high-nickel ternary cathode material is Ni 0.85 Co 0.083 Mn 0.040 Al 0.027 (OH) 2 The internal core material is Ni 90 Co 0.07 Al 0.03 (OH) 2 90% by mass, the outer shell material being Ni 0.40 Co 0.20 Mn 0.40 (OH) 2 10% by mass, the particle size (D50) is 6um; the lithium salt is a mixture of lithium hydroxide and lithium dihydrogen phosphate, wherein the lithium hydroxide accounts for the ratio by massIs 96 percent; the molar ratio of the lithium element in the lithium salt to the nickel-cobalt-manganese element in the high-nickel ternary cathode material precursor is 1.04; the phosphorus-containing additive is phosphorus pentoxide; the adding amount of the phosphorus-containing additive accounts for 0.5 percent of the mass of the precursor of the high-nickel ternary cathode material; the metal oxide additive is a mixture of zirconia and titania, wherein the mass ratio of the zirconia to the titania is 1; the materials are weighed according to the proportion and then put into a 10L high-speed mixer to be mixed for 60min;
(2) Putting the mixed material obtained in the step (1) into a sagger, putting the sagger into a high-temperature and high-pressure device for sintering, heating to 700 ℃ at the speed of 1.5 ℃/min, and setting the internal pressure of the device to be-7 Pa in the heating process; keeping the temperature for 6h after the temperature reaches 700 ℃, wherein the internal pressure of the device is 50Pa in the heat preservation process; then heating to 790 ℃ at the speed of 1.0 ℃/min, wherein the internal pressure of the device is-5 Pa in the heating process; keeping the temperature for 6h after the temperature reaches 790 ℃, wherein the internal pressure of the device is 10Pa in the heat preservation process; naturally cooling;
(3) And (3) grinding and sieving the material cooled in the step (2) to obtain the high-nickel anode material of the lithium ion battery.
The content of residual lithium, the pH value and the specific surface area of the material prepared in this example were measured, the content of residual lithium was measured by acid-base titration, the pH value was measured by a pH meter, the specific surface area was measured by a specific surface area meter, and the test results are shown in table 1.
An electron microscope image of the material obtained in this embodiment is shown in fig. 1, and it can be seen from the figure that: the surface primary particles are uniform, the secondary spheres have good compactness, and no obvious lithium residue exists on the surface;
the electrical properties of the material obtained in this embodiment are shown in fig. 2, and it can be seen from the figure that: the surface primary particles are uniform, the secondary spheres have good compactness, and no obvious lithium residue is left on the surface.
Example 2:
a preparation method of a high-nickel cathode material of a lithium ion battery comprises the following steps:
(1) Mixing a high-nickel ternary positive electrode material precursor, a lithium salt, a phosphorus-containing additive and a metal oxide additive; wherein is highThe precursor of the nickel ternary anode material is Ni 0.85 Co 0.083 Mn 0.040 Al 0.027 (OH) 2 The internal core material is Ni 90 Co 0.07 Al 0.03 (OH) 2 90% by mass, the outer shell material being Ni 0.40 Co 0.20 Mn 0.40 (OH) 2 10% by mass, the particle size (D50) is 10um; the lithium salt is a mixture of lithium hydroxide and lithium dihydrogen phosphate, wherein the mass ratio of the lithium hydroxide is 96%; the molar ratio of the lithium element in the lithium salt to the nickel-cobalt-manganese element in the high-nickel ternary cathode material precursor is 1.04; the phosphorus-containing additive is phosphorus pentoxide; the adding amount of the phosphorus-containing additive accounts for 0.5 percent of the mass of the precursor of the high-nickel ternary cathode material; the metal oxide additive is a mixture of zirconia and titania, wherein the mass ratio of the zirconia to the titania is 1; (ii) a The materials are weighed according to the proportion and then are put into a 10L high-speed mixer to be mixed for 60min;
(2) Putting the mixed material in the step (1) into a sagger, putting the sagger into a high-temperature high-pressure device for sintering, heating to 700 ℃ at the speed of 1.5 ℃/min, and setting the internal pressure of the device to be-7 Pa in the heating process; keeping the temperature for 6h after the temperature reaches 700 ℃, wherein the internal pressure of the device is 50Pa in the heat preservation process; then heating to 790 ℃ at the speed of 1.0 ℃/min, wherein the internal pressure of the device is-5 Pa in the heating process; keeping the temperature for 6h after the temperature reaches 790 ℃, wherein the internal pressure of the device is 10Pa in the heat preservation process; naturally cooling;
(3) And (3) grinding and sieving the material cooled in the step (2) to obtain the high-nickel anode material of the lithium ion battery.
This example differs from example 1 in that: the particle size (D50) of the precursor of the high-nickel ternary cathode material in the step (1) is 10um, and other steps are the same as those in the embodiment 1.
The residual lithium content, the pH value and the specific surface area of the material prepared in this example were measured, the residual lithium content was measured by acid-base titration, the pH value was measured by a pH meter, the specific surface area was measured by a specific surface area meter, and the test results are shown in table 1.
An electron microscope image of the material obtained in this embodiment is shown in fig. 3, and it can be seen from the figure that: the surface primary particles are uniform, the secondary spheres have good compactness, and no obvious lithium residue exists on the surface;
the electrical properties of the material obtained in this embodiment are shown in fig. 4, from which it can be seen that: the primary particles on the surface are uniform, the secondary balls have good compactness, and no obvious residual lithium is left on the surface.
Example 3:
the present example differs from example 1 in that: the particle size (D50) of the precursor of the high-nickel ternary cathode material in the step (1) is 15um, and other steps are the same as those in the embodiment 1.
The residual lithium content, the pH value and the specific surface area of the material prepared in this example were measured, the residual lithium content was measured by acid-base titration, the pH value was measured by a pH meter, the specific surface area was measured by a specific surface area meter, and the test results are shown in table 1.
Example 4:
the present example differs from example 2 in that: the molar ratio of the lithium element in the lithium salt in the step (1) to the nickel-cobalt-manganese element in the high-nickel ternary cathode material precursor is 1.02, and other steps are the same as those in the embodiment 2.
The residual lithium content, the pH value and the specific surface area of the material prepared in this example were measured, the residual lithium content was measured by acid-base titration, the pH value was measured by a pH meter, the specific surface area was measured by a specific surface area meter, and the test results are shown in table 1.
Example 5:
this example differs from example 2 in that: the molar ratio of the lithium element in the lithium salt in the step (1) to the nickel-cobalt-manganese element in the high-nickel ternary cathode material precursor is 1.06, and other steps are the same as those in the example 2.
The content of residual lithium, the pH value and the specific surface area of the material prepared in this example were measured, the content of residual lithium was measured by acid-base titration, the pH value was measured by a pH meter, the specific surface area was measured by a specific surface area meter, and the test results are shown in table 1.
Example 6:
the present example differs from example 2 in that: changing the step (2) of heating to 700 ℃ at a speed of 1.5 ℃/min and keeping the temperature for 6h after the temperature reaches 700 ℃ into the step (2):
"raise the temperature to 650 ℃ at 1.5 ℃/min, keep the temperature for 6h after the temperature reaches 650 ℃, other steps are the same as example 2.
The content of residual lithium, the pH value and the specific surface area of the material prepared in this example were measured, the content of residual lithium was measured by acid-base titration, the pH value was measured by a pH meter, the specific surface area was measured by a specific surface area meter, and the test results are shown in table 1.
Example 7:
this example differs from example 2 in that: changing the step (2) of heating to 700 ℃ at a speed of 1.5 ℃/min and keeping the temperature for 6h after the temperature reaches 700 ℃ into the step (2):
"raise the temperature to 750 ℃ at 1.5 ℃/min, keep the temperature for 6h after the temperature reaches 750 ℃, other steps are the same as example 2.
The content of residual lithium, the pH value and the specific surface area of the material prepared in this example were measured, the content of residual lithium was measured by acid-base titration, the pH value was measured by a pH meter, the specific surface area was measured by a specific surface area meter, and the test results are shown in table 1.
Example 8:
this example differs from example 2 in that: the precursor of the high-nickel ternary cathode material in the step (1) is Ni 0.85 Co 0.083 Mn 0.040 Al 0.027 (OH) 2 The internal core material is Ni 90 Co 0.07 Al 0.03 (OH) 2 90% by mass, the outer shell material being Ni 0.40 Co 0.20 Mn 0.40 (OH) 2 The mass ratio of 10 percent is changed into that:
the precursor of the high-nickel ternary positive electrode material is Ni 0.875 Co 0.0765 Mn 0.020 Al 0.0285 (OH) 2 The internal core material is Ni 90 Co 0.07 Al 0.03 (OH) 2 95% by mass of Ni as an outer shell material 0.40 Co 0.20 Mn 0.40 (OH) 2 Mass ratio of 5% ", and the other steps are the same as in example 2.
The residual lithium content, the pH value and the specific surface area of the material prepared in this example were measured, the residual lithium content was measured by acid-base titration, the pH value was measured by a pH meter, the specific surface area was measured by a specific surface area meter, and the test results are shown in table 1.
Example 9:
the present example differs from example 2 in that: the precursor of the high-nickel ternary cathode material in the step (1) is Ni 0.85 Co 0.083 Mn 0.040 Al 0.027 (OH) 2 The internal core material is Ni 90 Co 0.07 Al 0.03 (OH) 2 The mass percentage is 90 percent, and the material of the outer shell is Ni 0.40 Co 0.20 Mn 0.40 (OH) 2 The mass ratio of 10 percent is changed into that:
the precursor of the high-nickel ternary cathode material is Ni 0.825 Co 0.0895 Mn 0.060 Al 0.0255 (OH) 2 The internal core material is Ni 90 Co 0.07 Al 0.03 (OH) 2 85% by mass, the outer shell material being Ni 0.40 Co 0.20 Mn 0.40 (OH) 2 The mass ratio is 15% ", and other steps are the same as in example 2.
The content of residual lithium, the pH value and the specific surface area of the material prepared in this example were measured, the content of residual lithium was measured by acid-base titration, the pH value was measured by a pH meter, the specific surface area was measured by a specific surface area meter, and the test results are shown in table 1.
Example 10:
this example differs from example 2 in that: changing the mass ratio of lithium hydroxide to 96% in the step (1) into:
"the ratio of lithium hydroxide by mass was 98%", and the other steps were the same as in example 2.
The residual lithium content, the pH value and the specific surface area of the material prepared in this example were measured, the residual lithium content was measured by acid-base titration, the pH value was measured by a pH meter, the specific surface area was measured by a specific surface area meter, and the test results are shown in table 1.
Example 11:
this example differs from example 2 in that: changing the lithium salt in the step (1) into a mixture of lithium hydroxide and lithium dihydrogen phosphate, wherein the mass ratio of the lithium hydroxide is 96%:
the other procedure was the same as in example 2 except that "lithium salt was lithium hydroxide".
The residual lithium content, the pH value and the specific surface area of the material prepared in this example were measured, the residual lithium content was measured by acid-base titration, the pH value was measured by a pH meter, the specific surface area was measured by a specific surface area meter, and the test results are shown in table 1.
Example 12:
the present example differs from example 2 in that: changing the temperature of the step (2) to 700 ℃ and then preserving heat for 6h, wherein the internal pressure of the device in the heat preservation process is 50Pa into the following steps:
"the temperature is kept for 6h after the temperature reaches 700 ℃, the internal pressure of the device in the heat preservation process is 100Pa", and other steps are the same as the example 2.
The residual lithium content, the pH value and the specific surface area of the material prepared in this example were measured, the residual lithium content was measured by acid-base titration, the pH value was measured by a pH meter, the specific surface area was measured by a specific surface area meter, and the test results are shown in table 1.
Example 13:
this example differs from example 2 in that: changing the temperature of the step (2) to 700 ℃ and then preserving heat for 6h, wherein the internal pressure of the device in the heat preservation process is 50Pa into the following steps:
"the temperature was maintained for 6 hours after the temperature reached 700 ℃ and the internal pressure of the apparatus during the heat-preservation was 150Pa", and the other steps were the same as in example 2.
The content of residual lithium, the pH value and the specific surface area of the material prepared in this example were measured, the content of residual lithium was measured by acid-base titration, the pH value was measured by a pH meter, the specific surface area was measured by a specific surface area meter, and the test results are shown in table 1.
Example 14:
this example differs from example 2 in that: the molar ratio of the lithium element in the lithium salt in the step (1) to the nickel-cobalt-manganese element in the high-nickel ternary cathode material precursor is 1.00, and other steps are the same as those in the embodiment 2.
The content of residual lithium, the pH value and the specific surface area of the material prepared in this example were measured, the content of residual lithium was measured by acid-base titration, the pH value was measured by a pH meter, the specific surface area was measured by a specific surface area meter, and the test results are shown in table 1.
Example 15:
this example differs from example 2 in that: the molar ratio of the lithium element in the lithium salt in the step (1) to the nickel-cobalt-manganese element in the high-nickel ternary cathode material precursor is 1.10, and other steps are the same as those in the embodiment 2.
The residual lithium content, the pH value and the specific surface area of the material prepared in this example were measured, the residual lithium content was measured by acid-base titration, the pH value was measured by a pH meter, the specific surface area was measured by a specific surface area meter, and the test results are shown in table 1.
Example 16:
this example differs from example 2 in that: changing the adding amount of the phosphorus-containing additive accounting for 0.5 percent of the mass of the high-nickel ternary cathode material precursor in the step (1) into the following steps:
the addition amount of the phosphorus-containing additive accounts for 0.1 percent of the mass of the precursor of the high-nickel ternary cathode material, and other steps are the same as those in the embodiment 2.
The residual lithium content, the pH value and the specific surface area of the material prepared in this example were measured, the residual lithium content was measured by acid-base titration, the pH value was measured by a pH meter, the specific surface area was measured by a specific surface area meter, and the test results are shown in table 1.
Example 17:
this example differs from example 2 in that: changing the condition that the adding amount of the phosphorus-containing additive accounts for 0.5% of the mass of the high-nickel ternary cathode material precursor in the step (1) into the condition that:
the addition amount of the phosphorus-containing additive accounts for 1.5% of the mass of the precursor of the high-nickel ternary cathode material, and other steps are the same as those in the example 2.
The residual lithium content, the pH value and the specific surface area of the material prepared in this example were measured, the residual lithium content was measured by acid-base titration, the pH value was measured by a pH meter, the specific surface area was measured by a specific surface area meter, and the test results are shown in table 1.
Example 18:
the present example differs from example 2 in that: changing the lithium salt in the step (1) into a mixture of lithium hydroxide and lithium dihydrogen phosphate, wherein the mass ratio of the lithium hydroxide is 96%:
the lithium salt is a mixture of lithium oxalate and lithium phosphate, wherein the mass ratio of the lithium phosphate is 96% ", and other steps are the same as those in example 2.
The content of residual lithium, the pH value and the specific surface area of the material prepared in this example were measured, the content of residual lithium was measured by acid-base titration, the pH value was measured by a pH meter, the specific surface area was measured by a specific surface area meter, and the test results are shown in table 1.
Example 19:
this example differs from example 2 in that: changing the phosphorus-containing additive to phosphorus pentoxide in the step (1) into:
the "phosphorus-containing additive was ammonium dihydrogen phosphate", and the other steps were the same as in example 2.
The residual lithium content, the pH value and the specific surface area of the material prepared in this example were measured, the residual lithium content was measured by acid-base titration, the pH value was measured by a pH meter, the specific surface area was measured by a specific surface area meter, and the test results are shown in table 1.
Example 20:
this example differs from example 2 in that: changing the phosphorus-containing additive in the step (1) into phosphorus pentoxide:
the phosphorus-containing additive is a mixture of phosphorus pentoxide and ammonium dihydrogen phosphate, wherein the mass ratio of the phosphorus pentoxide is 20% ", and other steps are the same as in example 2.
The content of residual lithium, the pH value and the specific surface area of the material prepared in this example were measured, the content of residual lithium was measured by acid-base titration, the pH value was measured by a pH meter, the specific surface area was measured by a specific surface area meter, and the test results are shown in table 1.
Example 21:
this example differs from example 2 in that: changing the phosphorus-containing additive to phosphorus pentoxide in the step (1) into:
the "phosphorus-containing additive was a mixture of titanium phosphate, aluminum phosphate and phosphotungstic acid in the mass ratios of 20%, 20% and 60%, respectively," and the other steps were the same as in example 2.
The residual lithium content, the pH value and the specific surface area of the material prepared in this example were measured, the residual lithium content was measured by acid-base titration, the pH value was measured by a pH meter, the specific surface area was measured by a specific surface area meter, and the test results are shown in table 1.
Example 22:
this example differs from example 2 in that: the metal oxide additive in the step (1) is a mixture of zirconia and titania, wherein the mass ratio of the zirconia to the titania is 1; "change into:
the metal oxide additive is tungsten oxide, wherein the addition amount of the tungsten oxide accounts for 0.1% of the mass of the high-nickel ternary cathode material precursor, and other steps are the same as those in the embodiment 2.
The content of residual lithium, the pH value and the specific surface area of the material prepared in this example were measured, the content of residual lithium was measured by acid-base titration, the pH value was measured by a pH meter, the specific surface area was measured by a specific surface area meter, and the test results are shown in table 1.
Example 23:
this example differs from example 2 in that: the metal oxide additive in the step (1) is a mixture of zirconia and titania, wherein the mass ratio of the zirconia to the titania is 1; "change into:
the metal oxide additive is a mixture of tungsten oxide, titanium oxide and strontium oxide, wherein the mass ratio of tungsten oxide to titanium oxide to strontium oxide is 0.1%, 0.1% and 0.1%, the addition amount of the metal oxide additive is 0.5% of the mass of the high-nickel ternary cathode material precursor, and other steps are the same as those in example 2.
The residual lithium content, the pH value and the specific surface area of the material prepared in this example were measured, the residual lithium content was measured by acid-base titration, the pH value was measured by a pH meter, the specific surface area was measured by a specific surface area meter, and the test results are shown in table 1.
Example 24:
this example differs from example 2 in that: heating the temperature in the step (2) to 700 ℃ at a speed of 1.5 ℃/min, wherein the internal pressure of the device is-7 Pa in the heating process; keeping the temperature for 6h after the temperature reaches 700 ℃, wherein the internal pressure of the device is 50Pa in the heat preservation process; then heating to 790 ℃ at the speed of 1.0 ℃/min, wherein the internal pressure of the device is-5 Pa in the heating process; keeping the temperature for 6h after the temperature reaches 790 ℃, wherein the internal pressure of the device is 10Pa in the heat preservation process; "change into:
heating to 650 ℃ at a speed of 1 ℃/min, wherein the internal pressure of the device is-5 Pa in the heating process; keeping the temperature for 10 hours after the temperature reaches 650 ℃, wherein the internal pressure of the device is 80Pa in the heat preservation process; then heating to 750 ℃ at the speed of 0.5 ℃/min, wherein the internal pressure of the device is-8 Pa in the heating process; keeping the temperature for 10h after the temperature reaches 750 ℃, wherein the internal pressure of the device in the heat preservation process is 5Pa ", and the other steps are the same as those in the embodiment 2.
The content of residual lithium, the pH value and the specific surface area of the material prepared in this example were measured, the content of residual lithium was measured by acid-base titration, the pH value was measured by a pH meter, the specific surface area was measured by a specific surface area meter, and the test results are shown in table 1.
Example 25:
this example differs from example 2 in that: heating the temperature in the step (2) to 700 ℃ at a speed of 1.5 ℃/min, wherein the internal pressure of the device is-7 Pa in the heating process; keeping the temperature for 6h after the temperature reaches 700 ℃, wherein the internal pressure of the device is 50Pa in the heat preservation process; then heating to 790 ℃ at the speed of 1.0 ℃/min, wherein the internal pressure of the device is-5 Pa in the heating process; keeping the temperature for 6h after the temperature reaches 790 ℃, wherein the internal pressure of the device is 10Pa in the heat preservation process; "change into:
heating to 780 ℃ at 3 ℃/min, wherein the internal pressure of the device is-10 Pa in the heating process; keeping the temperature for 4h after the temperature reaches 780 ℃, wherein the internal pressure of the device is 200Pa in the heat preservation process; then heating to 850 ℃ at the speed of 2 ℃/min, wherein the internal pressure of the device is-10 Pa in the heating process; keeping the temperature for 4h after the temperature reaches 850 ℃, wherein the internal pressure of the device is 50Pa in the heat preservation process, and the other steps are the same as the steps in the embodiment 2.
The residual lithium content, the pH value and the specific surface area of the material prepared in this example were measured, the residual lithium content was measured by acid-base titration, the pH value was measured by a pH meter, the specific surface area was measured by a specific surface area meter, and the test results are shown in table 1.
Table one is shown below:
Figure BDA0003902108450000121
Figure BDA0003902108450000131
TABLE 1
As can be seen from the data in table 1:
compared with the scheme 1/2/3, the comparison shows that when the particle sizes of the precursors are different, the larger the particle size is, the lower the specific surface area of the material is, and the higher the residual lithium is, which may be caused by the fact that when the particle size is too large, the difficulty in transferring lithium ions into the structure is high, the surface residue is relatively high, the pH value is not changed obviously, and the more lithium phosphate is possibly remained on the surface of the material;
compared with the scheme 2/4/5, the proportion of lithium is different, the residual lithium tends to rise along with the increase of the proportion coefficient, but the pH value and the specific surface area are not obviously changed;
compared with the scheme 2/6/7, when the low-temperature sintering temperature is different, residual lithium and the pH value tend to decrease first and then increase along with the increase of the sintering temperature, and probably, divalent nickel is most easily oxidized into trivalent nickel at the temperature, so that lithium ions are more favorably transferred into the structure;
compared with the scheme 2/8/9, when the nickel content is different, the residual lithium and the pH value are in a rising trend along with the rising of the nickel content, the shell is probably thinner, the nickel content is higher, the difficulty of oxidizing bivalent nickel into trivalent nickel is higher, and lithium ions are not facilitated to migrate into the structure;
as can be seen by comparing the scheme 2/10/11, the increase of the usage amount of the lithium hydroxide in the proportioning process has no obvious influence on residual lithium and pH value;
as can be seen from the comparison of schemes 2/12/13, during low-temperature sintering, the residual alkali tends to decrease with the supply of pressure, probably because increasing the pressure is favorable for the oxidation of divalent nickel into trivalent nickel and is more favorable for lithium ions to migrate into the structure.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
The above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. A preparation method of a high-nickel cathode material of a lithium ion battery is characterized by comprising the following steps:
(1) Mixing a high-nickel ternary positive electrode material precursor, a lithium salt, a phosphorus-containing additive and a metal oxide additive; the molar ratio of the lithium element in the lithium salt to the nickel-cobalt-manganese element in the high-nickel ternary positive electrode material precursor is 1.00-1.10; the addition amount of the phosphorus-containing additive accounts for 0.1-1.5 wt% of the mass of the high-nickel ternary cathode material precursor; the addition amount of the metal oxide additive accounts for 0.1-0.5 wt% of the mass of the high-nickel ternary cathode material precursor;
(2) Putting the mixed material obtained in the step (1) into a sagger, putting the sagger into a high-temperature and high-pressure device for sintering, and naturally cooling the sagger after sintering;
(3) And (3) grinding and sieving the material cooled in the step (2) to obtain the high-nickel anode material of the lithium ion battery.
2. The method for preparing the high-nickel cathode material of the lithium ion battery according to claim 1, wherein the chemical formula of the precursor of the high-nickel ternary cathode material is Ni x Co y Mn z Al 1-x-y-z (OH) 2 Wherein x is more than or equal to 0.8 and less than or equal to 0.9, y is more than or equal to 0.05 and less than or equal to 0.15, z is more than or equal to 0.01 and less than or equal to 0.10, and x + y + z is more than or equal to 0.95 and less than or equal to 0.99.
3. The preparation method of the high-nickel cathode material for the lithium ion battery according to claim 1 or 2, wherein the particle size D50 of the precursor of the high-nickel ternary cathode material is 6-15um.
4. The method for preparing the high-nickel cathode material of the lithium ion battery according to claim 3, wherein the lithium salt is one or a combination of two of lithium hydroxide, lithium oxalate, lithium dihydrogen phosphate and lithium phosphate; the phosphorus-containing additive is one or the combination of more of ammonium dihydrogen phosphate, phosphorus pentoxide, titanium phosphate, aluminum phosphate and phosphotungstic acid.
5. The method for preparing the high-nickel cathode material for the lithium ion battery according to claim 4, wherein the metal oxide additive is a metal oxide additive with a metal ion radius of 60-80 pm.
6. The method for preparing the high-nickel cathode material of the lithium ion battery according to claim 1, wherein the metal oxide additive is one or more of zirconium oxide, tungsten oxide, titanium oxide and strontium oxide.
7. The method for preparing the high-nickel cathode material of the lithium ion battery according to claim 1, wherein the sintering in the step (2) is gradient sintering, and the low-temperature sintering is performed first, and then the high-temperature sintering is performed.
8. The method for preparing the high-nickel cathode material of the lithium ion battery according to claim 7, wherein the low-temperature sintering specifically comprises: heating to 650-780 ℃ at the heating rate of 1-3 ℃/min under the pressure of-10 to-5 Pa, and preserving heat for 4-10 h, wherein the pressure in the heat preservation process is 50-200 Pa.
9. The method for preparing the high-nickel cathode material for the lithium ion battery according to claim 7, wherein the high-temperature sintering specifically comprises the following steps: heating to 750-850 ℃ at the heating rate of 0.5-2 ℃/min under the pressure of-10 to-5 Pa, and preserving heat for 4-10 h, wherein the pressure in the heat preservation process is 5-50 Pa.
10. The high-nickel cathode material for the lithium ion battery prepared by the preparation method according to any one of claims 1 to 9.
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